Addition agent for lubricating oils



atented Jan. as. 1943 2,309,33

UNITED STATES PATENT OFFICE 2.30am r r annrnos seam. roa wmnca'rme oms Gordon b. Byrkit, Ponca City. on, assignor to Continental Oil Company, Ponca City, Okla, a corporation of Delaware 1 no Drawing. Application August 26, 1938,

Serial No. 226,966

My invention relates to an addition agent for ubricating oils and to an improved lubricating ail formed therefrom.

This application is a continuation in part of lubricantshas the very important property of reacting with the metal surfaces, penetrating and/or adsorbing on the metal, leaving a film of lubricant with high oiliness characteristics, which remains on the metal surface irrespective of the 5 Claims. (Cl. 260-410) length of time the machine has been idle. This high oiliness film gives very smooth operation, which may be easily discerned by the experienced operator and lubricating engineer.

my copending application, Serial No. 87,464, filed 5 One object of my invention is to provide mate- June 26, 1938. rials, which when added to mineral lubricating Present day mechanical devices require lubrioils improve their oiliness and load-carrying eating oils of high film strength. It has been ability and enable the oil to lower the friction found that the highest quality straight hydrobetween the rubbing surfaces. carbon lubricants have a film strength insuiii- Another object of my invention is to provide cient for eilicient use inpresent day, mechanical a. material, which when blended with the hydevice's. High quality straight hydrocarbon drocarbon oils will produce a lubricant which lubricants used under conditions of high pre'swill maintain a very low coefficient of friction sure, low speed and/or high temperatures, have when diluted with light hydrocarbons such as a tendency to break down due to their low'film are obtained in an automobile crankcase by strength. with high pressures between the rubincomplete combustion of the fuel. bing surfaces, the body of the lubricant is A further object of my invention is .to provide squeezed out and only a thin film remains. It a material which when blended with hydrois readily seen that with a low fllm strength lubrlcarbon lubricants will confer upon it penetrative cant, there is a tendency for the lubricant to l ri i y chara teristi s. It has be n found that break down, decompose, and allow the rubbing y m P a lubricant is Produced wh h surfaces to come in contact and cause seizure. does not drain of! the rubbing surfaces when It is well known that mineral lubricating oils idle, thereby providing a lubricating him on the are deficient in oiliness, which is the most imrubbing surfaces at all times and being of great portant character of the lubricant when used value to the life of the machine in cold-weather under conditions of boundary lubrication where starting, when the lubricant is very stiff and the viscosity of the lubricant plays little or no sluggish. part. Boundary lubrication conditions are ob- A still further object of my invention is to tained when engines are operating at heavy provide a material, which when blended with loads, low speed, or if for any reason the supply a. lubricant enables it to produce a more nearly of lubricant is cut on or not suiiicient. This last constant coeflicient of friction, thereby in i condition may exist when for mechanical reasmoother engine p rflt onr 7 sons the lubricant pump is not functioning prop- It is well known to the art that the addition erly or when the lubricant feed line is clogg'ed of certain chlorinated or otherwise halo n ted with foreign matter, organic materials to mineral lubricants improves Instarting idle mechanical equipment which is the character of the latter in these various re- :lubricated from a sump by pumping or circulatspects. For example, U. 8. Patent 1,944,941, ing the lubricant, there is always a short period issued to Bert H. Lincoln and Alfred Henriksen of time in which the rubbing surfaces must operm 1934, describes a hlhr lh! 11 ate under conditions of dry friction if ordinary 40 1 comprising in combination a hydro arbon Oil hydrocarbon lubricants are used. With dry fricand a small quant ty o certai halo enated tion the wear on friction surfaces is extreme, and t r wh h improve he blunt-"l8 and loadduring cold weather, when the lubricant is slugcarrying ability of the mineral oil. 6 11 1119 11 gish or during periods when th lubricating it penetratlve lubricity characteristics and enable system is not functioning properly for ne reason it to reduce the. coefficient of friction between or another, rubbing surfaces may not only suffer rubbing surfaces. considerable wear but may be damaged to the I hav found that material excellently suited where they must be replaced. By means r th purpose of improving these characterisof my inventlon, it is possible to produce a matics of hydr r 011 m y be t i y the terial fwhich when blended with hydrocarbon interaction of various chlorinated waxes with anhydrous metal salts of organic acids. The chlorinated or otherwise halogenated wax may be prepared from hydrocarbon paraffin wax or from naturally occurring ester-like waxes such as carnauba wax or from synthetic wax-like esters drocarbons and invariably contain unchlorinated hydrocarbons, monochlorinated hydrocarbons, dichlorinated hydrocarbons, and polychloro hydrocarbon derivatives. For example, a so-called "trichloro parafiln wax" containing 24 percent chlorine, which corresponds closely to the percentage of chlorine in the trichloro compound, was separated by means of crystallization from acetone. The least soluble portion "consisted of unchlorinated wax. The next least soluble portion consisted of a mixture of monochloro wax and unchlorinated wax. The percentage of unchlorinated wax in the original mixture was found to be 7.2 percent. Thus, even in a "trichloro para so-called, of the prior art, there is a large percentage of unchlorinated 'wax and ture containing as quantities of monochlorinated wax and dichlorinated wax, besides trichlor wax and more highly chlorinated waxes.

In carrying out the method of my invention,-the use of a crude mixture of chlorinated waxes will not give the same results as a substantially pure chlorinated wax. Even though the appropriate amount of chlorine is introduced into a wax to form a monochloro wax, the crude chlorination mixture will contain in addition to small amounts of chlorine and hydrogen chloride, and the desired monochlor wax, unchlorinated wax and more highly chlorinated waxes. Y

I have found that, on introducing chlorine into the higher paraiiin hydrocarbons, as for example, paraifin wax, the formation of the diand higher poly-chlor waxes begins when only 5 percent by weight of chlorine has. been introduced into the parafiln hydrocarbon. This formation of di-, and higher poly-chlor waxes proceeds more rapidly than the chlorination of the hydrocarbon to the'monochlor compound so that the proportion of the latter in a crude chlorinated mixture decreases rapidly and is at a maximum when about 10 percent of chlorine has been introduced. At this point, a typical chlorinated mixture will contain about 25-30 percent of'unchlorinated wax,

40-50percent of monochlor wax, percent of dichlor wax, as well rinated waxes.

and about 20-25 as higher chlo- Even when as much as 24 percent by weight of'chlorine is introduced into a paraffin wax, about 10 percent of unchlorinated hydrocarbon is still present in the mixture. The removal of unchlorinated hydrocarbons from the crude chlorinated mixture is the first step in preparing relatively pure monohalogen compounds, and higher halogenated compounds, but it will be obvious that the chlorine compounds, when separated from the unchlorinated hydrocarbon, form a crude mixture of hydrocarbons in various stages of chlorination.

The chlorination of most petroleum hydrocarbons lowers their melting points and, to a certain degree, the greater the extent, of chlorination, that is to the more chlorine atoms per molecule,

the lower the melting point. The decrease in is stepwise. This permits me to separate unchlorinated hydrocarbons from the monochlor hydrocarbons, the monchlor hydrocarbons from the dichloro hydrocarbons, and the dichloro hydrocarbons from the trichloro hydrocarbons. Having selected the hydrocarbon in accordance with the desired final product, I chlorinate the hydrocarbons until approximately that amount of chlorine is absorbed which will produce monochlor compounds, if these are desired, or larger amounts of chlorine to produce (11-, and higher poly-chloro hydrocarbons when these products are desired. For example, in the manufacture of a monochloro hydrocarbon containing 18- 24 carbon atoms per molecule, I select a paraffin wax having a melting point of approximately 120 F. I introduce into this wax about 10 percent of added chlorine which will form a mixan average about the same weight of chlorine as the monochlor product. This may vary from not less than 8 to not more than 12 percent, without being disadvantageous. The percentage of chlorine introduced into the hydrocarbon will be less in the case of the higher molecular weight, higher melting hydrocarbons. The chlorination may be accomplished by any suitable method and any appropriate apparatus. I prefer to melt the wax and agitate thoroughly, while the chlorine gas is introduced into contact therewith so as to be well distributed through the liquid. The heat of reaction is ordinarily ample to maintain the mixture in the liquid state without further heating. I make provision for the escape of quantities of hydrogen chloride gas which are evolved, and for unreacted chlorine. When a sufiicient quantity of chlorine has been introduced, I blow the mixture with air or other inert gas such as carbon dioxide until the hydrogen chloride and free chlorine are substanially removed.

Even though the appropriate amount ofchicrine is introduced into the. wax to form a monochlor wax, as I have pointed out above, it will be found that the crude chlorination mixture contains in addition to the byproduct hydrogen chlode and the desired monochlor wax, also unchlorinated wax and more highly chlorinated waxes.

The unchlorinated wax is separated from the air blown mixture by pressing at such temperature that the chlorinated waxes are largely liqum and the unchlorinated wax is mostly solid. The appropriate temperature to which the mixture must be chilled before the pressing operation begins will depend upon the character of the hydrocarbon used initially, and may vary considerably. For example, when a wax having a melting point of 120 F. is used as the starting material, a temperature of about -90 F, is suitable for the separation of unchlorinated wax from the mixture.

Other separation processes, for example,

sweating, may be employed to separate the solid,

unchlorinated wax from the liquid chlorinated waxes.

The liquid chlorinated waxes will consist large- These may be separated by crystallization from acetone or any other suitable solid, using 'a solvent-chlor wax ratio of from 1' to 1 to 20 to 1. The solution is prepared by warming and is then chilled to approximately 15 to 20 F. to precipitate the chlorinated waxes which are then removed by filtering, pressing, settling, or in any other suitable manner.

The monochlor wax is precipitated out of the solution nearly quantitatively and its separation from the dichlor and polychlor waxes present is readily accomplished.

Instead of acetone, such selective solvents as methylethyl ketone, acetone-benzene mixtures, acetone-methylene chloride mixtures or various halogenated solvents may be employed. It will be obvious that the quantity oi solvent and the temperature to which the solution should be chilled will depend upon the particular materials being processed and may be readily determined empirically. The halogenated solvents serve to aid in the precipitation oi unchlorinated waxes, while benzene increases the solubility of the more highly chlorinated materials.

The monochlor wax thus obtained was found to contain approxirnatelythe theoretical chlorine content. Various batches show chlorine contents of 10.1, 10.5, 10.3, and 10.8 percent. The theoretical chlorine content is 10.2 percent so that it will be apparent that the monochlor wax obtained is substantially free from unchlorinated waxes and highly chlorinated waxes. The monochlor wax was found to behave very much like a pure compound. I proved the homogeneity of my monochlor wax. for example, by chilling until approx mately half of the material had solidifled. Solid and liquid portions were separated by filtration and contained 12.1 and 11.4 percent chlorine respectively. My monochlor wax is therefore free from both unchlorinated wax and more highly chlorinated wax. Similarly, I may prepare according to my invention diand polychloro waxes free from unchlorinated wax and monochlor wax, as well as more highly chlorlnated waxes.

Any of the relatively pure chlorinated waxes may be used in carrying out my invention. One

of these waxes is condensed with the anhydrous metal salt oi an organic acid. The organic acid may be of am type: that is. aliphatic, aromatic, or heterocyclic or may belong to more than one of these classes. I have found that the use of halogenated or an c acids for this purpose gives products which are particularly eiflclent in improving the c aracter st cs of mineral lubrieating all when blended with them. The chosen organic acid is converted to the sodium salt or other metallic salt by means 01 neutralization with a suitable base such as sodium hydroxide. barium hydroxide. etc., and rendered anhydrous by intensive dryin or. if necessary, fusion.

Our condensation products are of several types depending on the structure of the starting materials:

I. Esters from monohalogen compounds:

A. Esters from monohalogenated hydrocarbons. These are esters of the type RCOrR' derived from the metal salt, RCOaM, and the halogenated hydrocarbon,

R'X.M represents a metal; X repre- 4. Monochloro-gasoline bons 5. Monochloro-kerosene hydrocarbons B. Diesters from monohalogenated esters. These are of three types depending on the position of the halogen.

esters are distinguished in that they hydrolyze to form an alcohol, R-"OH, an acid, R'COzH, and a hydroxy acid,

RCHOH (CH2) nCOzH Examples of monohalogenated esters which may be used are:

a.0ctadecy1 aipha-bromostea rate b. Monochloro-carnauba wax c. Monochloro-beeswax 2. Halogen in the alcohol radical.

These esters are oi the type, RCO2R'O.CO.R", derived irom the metal salt R"CO:M and the monochloro-ester, RCOaR/X in which R is a divalent organic radical. These esters are distinguished in that they hydrolyze to form two acids, RCOzH and R"COaH and a glycol, R/(OH): which may be vicinal or disjoined depending on the position of the halogen. Examples of monohalogenated esters which may be used are= a. Beta-chloroethyl stearate b. Monochloro-octadecyl stearate 0. Monobromo-carnauba wax II. Esters from dihalogen compounds:

A. :Esters from dihalogenated hydrocarbons. These esters are of the type,

(RCOzhR', in which R .is a divalent organic radical, derived from the metal salt, RCOaM, and the dihalogenated hydrocarbon, R'Clz. These esters are distinguished in that they hydrolyze to form an acid, RCOzH, and a ketone if both halogen atoms in R'Cla are on the same carbon atom; an acid and a.

vicinal glycol it the halogens are on adjoining carbon atoms; and an acid and a disjoined glycol if the halogens are on disjoined carbon atoms. Examples of dihalogenated hydrocarbons which may be used are:

3,3-dichlorodecane 2,3-dichlorodecane 1,10-dichlorodecane Dichloroparaflln wax Dibromo-gasollne hydrocarbons Dichloro-kerosene hydrocarbons .B. Esters from dihalogenated esters.

These are of three classes containing several types depending on the position of the halogen atoms.

1. Bothl halogens in the alcohol radica These esters are it the type. RCOaR' (0.003") a in which R is a trivalent organic radicals Theesters are derived from the dichloro-esters RCOzR'Ch. These esters are distinguished in that they hydrolyze to form two acids,

RCOzH and R"CO:H, and a trihydroxy organic R'(OH)a or'a hydroxyketone. Examples of dihalogenated esters which may be used are:

a. 2,2-dichloroethyl stea'rate b. Dichloro-carnauba wax c. Dichloro-candelilla wax 2. Both halogens in the acid radical.

These esters are of the ype, (RG01): R'COzR", in which R is a trivalent organic radical. The dichloro-esters from which these are derived ha ve th e formula R"Clz.CzR". These esters are distinguished in that they hydrocompound lyze to form an alcohol, R"0H, an

acid, RCOzH, and a dlhydroxyacid R'(OH)2CO2H or a keto-acid if both halogens were originally on the same carbon atom. Examples of dihalogenated esters which may may be used are:

a. Methyl alpha, alpha-dichlorostearate b. Dichloro-beeswax c. Dibromo spermaceti d. Methyl alpha, beta-dichlorostearate e. Ethyl cinnamate dibromide 1. Methyl alpha, iota-dichlorostearate 3. One halogen in each radical.

These esters are of the type,-

RCOzR'CO: R".O.COR in which R and R" are divalent organic radicals. The starting chloro-esters have the formula R'Cl.CO:R"Cl. These esters are distinguished in that they, ydrolyze to form an acid, RCOzH, a hydroxyacid, R'(OH) 002K, and a glycol, R"(OH)2 which may be vicinal or disloined depending on the position of the original halogen atoms. Examples of dihalogenated esters which may be used are:

a. Beta-chloroethyl alpha-chlorostearate b. Gamma chloropropyl iotachlorostearate c. Dichloro-candelilla wax III. Esters from polyhalogen compounds The products of our invention may or may not contain halogen from one or both of two sources depending on the starting materials and their treatment. The halogen compound may be treated so as to remove all or only part of the halogen. Furthermore, the acid whose sodium or other metal salt is used in the condensation may or may not contain halogen itself. Halogen from this source will remain in the final product. For example, we may use sodium o-chloro-benzoate as a reagent or we may use a chlorwax containing 23 percent halogen and treat it with insuflicient quantities, of metal salt or for insuflicient time or at too low a temperature to remove all the halogen from the chlorwax. In order to obtain substantially halogen-free esters as :flnal products, we treat our halogen compound at a suillciently high temperature for a suflicient time with a suitable excess of a halogen-free sodium salt as described below.

For use in lubricating oils, it is desirable that the compounds employed should have a vapor pressure of less than atmospheric at a temperature of about 250' F. Compounds having this vapor pressure will not vaporize during use in an. internal combustion engine or as a crank case lubricant.

'I'hecondensation of the chlorinated wax' with the anhydrous sodium salt is eifected by heating these two components in the presence of small amounts of an acid anhydride and a tertiary base.

such as pyridine, or dimethylaniline. If the organic acid used is cheaply available in the form of the anhydride, that anhydride is preferable used as a condensing agent; thus, for example, if acetic acid is used to prepare the anhydrous sodium salt, then acetic anhydride is preferably used as the condensing anhydride; however, acetic or any other cheaply available acid anhydride is suitable to effect the condensation.

The use of a tertiary base such as pyridine or imethylaniline serves to increase the rate of reaction between the components so as to effect the condensation in a shorter time. In general, the condensation is efi'ected by heating the components to a temperature of from to 200 degrees 0., usually about 140 degrees C. for 8 to 16 hours however in the presence of the tertiary base, the condensation is completed in a much shorter time; namely, from 4 to 8 hours at this temperature.

The condensation product is separated from the reaction mixture by washing with water and drying the product by any suitable means, such as, for example, blowing with air at an elevated temperature.

The resulting condensation product is blended with a hydrocarbon oil of any character and the resulting blend is considerably improved in film strength oiliness and penetrative lubricity characteristics. The coefilcient of friction between rubbing metals lubricated by the blend is considerably lower than the coeilicient of friction when the straight hydrocarbon lubricant is used.

Various types of lubricants are susceptible to treatment by this invention, including paraflln base. naphthenic base and/or asphaltic base hydrocarbon oils and other oils of lubricating viscosity such as animal and vegetable oils, namely, castor oil, sperm oil, cottonseed oil, lard oil, corn oil, and synthetic oils including hydrogenated oils.

The following example of my invention is given to show one embodiment thereof, but it is to be understood that my invention is not limited thereto except in so far as pointed out in the claims. All quantities are given in parts by weight. parts of a relatively p'ure monochlor wax was heated with 58 parts of the anhydrous sodium salt of chloroacetic acid and 47 parts of free choloracetic acid in the presence of five ml. of acetic anhydride and 2 ml. of pyridine at to C. for 6 hours. The resulting condensation product was washed with water and dilute sodium carbonate solution to remove free acids and dried by air blowing at 140 F. This condensation product when blended with 99 parts by weight of a hydrocarbon oil greatly improved the load carrying ability, oiliness and penetrative lubricity characteristics and reduced the coefficient of friction between rubbing metal surfaces.

ted material, but it is to be understood that my 01' the halogens are suitable in the preparalon of my condensation product. For example, .uorine, bromine, or iodine may be used; but ince chlorine is so cheaply available, it is the referred embodiment of my invention.

It will be understood that certain features and ub-combinations are of utility and may be emiloyed without reference to other features and tub-combinations. This is contemplated by and 5 within the scope of my claims. It is further )bViOllS that various changes may be made in ietail within the scope of my claims without ieparting from the spirit of my invention. It is aherefore to be understood that my invention is not to be limited to the specific details shown and described.

Having thus described my invention, 1 claim:

1. As an addition agent for the improvement of the lubricating qualities of a hydrocarbon oil, a synthetic material obtained by condensing a relatively pure homogeneously chlorinated wax with an anhydrous sodium salt of an organic acid in the presence of an organic acid anhydride and a tertiary base.

2. A synthesis method for 25 the preparation of addition agents for lubricating oils, including the steps or condensing a relatively pure homogeneously chlorinated wax with an anhydrous metal salt of an organic acid in the presence of an organic acid anhydride.

3. A synthesis method for the preparation of addition agents for lubricating oils including the steps of condensing a, relatively pure homogeneously chlorinated wax with an anhydrous metal salt of an organic acid in the presence of an organic acid anhydride and a tertiary base.

4. A method of synthesizing addition agents for use in improving the lubricating qualities of hydrocarbon oils, including the step of condensing a relatively pure homogeneously chlorinated wax with an alkali metal salt of an organic acid in the presence of an acid anhydride and a tertiary base.

5. A method of making an addition agent for hydrocarbon oils including the step of condensing a relatively pure homogeneously chlorinated wax with anhydrous sodium chloro acetate in the presence of acetic anhydride and pyridine.

GORDON D. BYRKIT. 

